WO2011077810A1

WO2011077810A1 - Cylinder lubricant oil composition for crosshead-type diesel engine

Info

Publication number: WO2011077810A1
Application number: PCT/JP2010/067770
Authority: WO
Inventors: 茂樹竹島; 直純有本
Original assignee: Ｊｘ日鉱日石エネルギー株式会社
Priority date: 2009-12-24
Filing date: 2010-10-08
Publication date: 2011-06-30
Also published as: US20120258897A1; JP2011132338A; CN102666819A; EP2518134B1; CN102666819B; KR20120109578A; EP2518134A4; SG181735A1; US9222054B2; JP5483329B2; EP2518134A1; KR101728191B1

Abstract

Disclosed is a cylinder lubricant oil composition for a crosshead-type diesel engine, which has improved stability to oxidation and improved scuffing resistance besides the properties of the conventional cylinder lubricant oil compositions. The cylinder lubricant oil composition is characterized by comprising (A) an alkali earth metal finate in an amount of 0.005 mol/kg or more in terms of finate soap content, (B) an amine-type antioxidant agent in an amount of 0.1 to 5% by mass, and (C) an oil-soluble molybdenum compound in an amount of 30 to 500 ppm by mass in terms of molybdenum element content in a base oil having an aromatic component content of 8.5 % by mass or more (wherein all of the amounts are expressed relative to the total amount of the composition), wherein the composition has a base value of 20 to 100 mgKOH/g and a kinematic viscosity of 12.6 mm²/s or more at 100˚C.

Description

Cylinder lubricating oil composition for crosshead type diesel engine

The present invention relates to a cylinder lubricant composition for a crosshead type diesel engine.

¡Cylinder oil that lubricates between the cylinder and piston and system oil that controls lubrication and cooling of other parts are used in the crosshead type diesel engine. The cylinder oil is required to have a proper viscosity necessary for lubrication between the cylinder and the piston (piston ring) and a function of maintaining cleanliness necessary for proper movement of the piston and piston ring. Furthermore, this engine has a problem of cylinder corrosion due to acidic components such as sulfuric acid generated by combustion because high sulfur fuel is usually used because of its economic efficiency. In order to prevent this problem, the cylinder oil must have a function of neutralizing acidic components such as sulfuric acid to prevent corrosion.

On the other hand, in order to further improve the performance of recent crosshead type diesel engines, the cylinder diameter is increased (for example, bore size is 70 cm or more) and the piston stroke is increased (for example, the average piston speed is 8 m / s or more). There is a tendency to increase the combustion pressure (for example, net effective pressure (BMEP) 1.8 MPa or more), leading to an increase in the piston and cylinder wall temperature. An increase in combustion pressure leads to an increase in the dropping point of sulfuric acid, so that sulfuric acid corrosion of the cylinder is likely to occur. Furthermore, as a measure for preventing this sulfuric acid corrosion, there is a tendency to increase the cylinder wall temperature (for example, the cylinder wall temperature is 250 ° C. or higher), and the amount of lubricating oil injected into the cylinder is being reduced for economic reasons. For this reason, the lubrication environment of cylinders has become more severe. With such environmental changes, it has become an urgent task to improve scuffing resistance (Patent Documents 1 and 2).

Since cylinder oil is a total loss type lubricating oil, oxidation stability has not been omitted so far (Patent Document 1, Patent Document 2). The present inventors have found that not only the antioxidant property but also the scuffing resistance is remarkably improved by adding a specific antioxidant. On the other hand, in order to improve oxidation stability in lubricating oils, it is known to use base oils with less aromatic components or to add antioxidants. Moreover, it is known that a molybdenum compound acts as an antioxidant (Patent Document 3 and Patent Document 4). According to Patent Document 3, crankcase oil obtained by adding an oil-soluble molybdenum compound from which sulfur has been removed, an oil-soluble diarylamine and an alkaline earth metal phenate to a hydrocracking base oil has good oxidation stability and reduces tappet wear. And reducing ring and valve deposits. Patent Document 4 discloses that a base oil having an aromatic component of 3.0% by weight or less contains alkyldiphenylamines and / or phenyl-α-naphthylamines, sulfurized oxymolybdenum dithiocarbamate and / or sulfurized oxymolybdenum organophosphorodiate. Discloses that the lubricating oil has high heat resistance, high oxidation stability and low friction.

JP 2008-239774 A JP 2007-197700 A Japanese Patent No. 3507915 Japanese Patent No. 3608805

The present invention is to provide a cylinder lubricating oil composition for a crosshead type diesel engine which has improved oxidation stability and scuffing resistance in addition to conventional performance.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an alkaline earth metal phenate, an amine-based antioxidant, and an oil-soluble molybdenum compound are added to a base oil having an aromatic content of 8.5% by mass or more. Has been found to be effective as a cylinder lubricating oil composition for a crosshead type diesel engine, and the present invention has been completed.

That is, the present invention provides (A) an alkaline earth metal phenate as a phenate soap content in a base oil having an aromatic content of 8.5% by mass or more based on the total amount of the composition. As described above, (B) 0.1 to 5% by mass of the amine-based antioxidant and (C) 30 to 500 mass ppm of the oil-soluble molybdenum compound in terms of molybdenum element, and the base number of the composition is 20 to 100 mgKOH / g, kinematic viscosity at 100 ° C. is 12.6 mm ² / s or more, and relates to a cylinder lubricating oil composition for a crosshead type diesel engine.

The present invention also relates to the cylinder lubricating oil composition for a crosshead type diesel engine as described above, wherein (B) the amine-based antioxidant is alkyldiphenylamine and / or N-phenyl-α-naphthylamine.

The present invention also relates to (C) the cylinder lubricating oil composition for a crosshead type diesel engine as described above, wherein the oil-soluble molybdenum compound is molybdenum dithiocarbamate and / or molybdenum dithiophosphate.

The present invention further relates to the cylinder lubricating oil composition for a crosshead type diesel engine as described above, further comprising (D) an ashless dispersant in an amount of 1 to 8% by mass based on the total amount of the composition.

The lubricating oil composition of the present invention is excellent in scuffing resistance, heat resistance, and oxidation stability, and is suitable as a cylinder lubricating oil composition for a crosshead type diesel engine. In particular, the average piston speed is 8 m / s or more. Is a super long stroke of 8.5 m / s or more, the combustion pressure is a net effective pressure (BMEP) of 1.8 MPa or more, further 1.9 MPa or more, the maximum cylinder wall temperature 230 ° C. or more, and 250 It exhibits particularly excellent effects as a cylinder lubricating oil composition for an electronically controlled two-stroke cycle diesel engine that is operated under a condition that satisfies any or all of the conditions such as ℃ or higher, particularly 270 ℃ or higher.

Hereinafter, the present invention will be described in detail.
There is no particular limitation on the type of the lubricating base oil used in the cylinder lubricating oil composition for a crosshead type diesel engine of the present invention (hereinafter simply referred to as the lubricating oil composition of the present invention). Mineral oil, synthetic oil or these Mixtures can be used.

Specifically, as the mineral base oil, the lubricating oil fraction obtained by subjecting the crude oil to atmospheric distillation obtained under reduced pressure is subjected to solvent removal, solvent extraction, hydrocracking, Produced by one or more processes such as solvent dewaxing, hydrorefining, etc., or manufactured by a method of isomerizing GTL WAX (Gas Liquid Wax) produced by wax isomerized mineral oil, Fischer-Tropsch process, etc. Lubricating oil base oil and the like can be exemplified.

Specific examples of synthetic base oils include polybutene or hydrides thereof; poly α-olefins such as 1-octene oligomers and 1-decene oligomers or hydrides thereof; ethylene and α-olefins having 2 to 30 carbon atoms Diesters such as ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate; trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol -Polyol esters such as 2-ethylhexanoate and pentaerythritol pelargonate; Copolymers of dicarboxylic acids such as dibutyl maleate and α-olefins having 2 to 30 carbon atoms; Alkyl naphthalene, alkyl benzene, aromatic ester It can be exemplified Le aromatic synthetic oils, or mixtures of these and the like, and the like.

As the lubricating base oil used in the lubricating oil composition of the present invention, a mineral base oil or a synthetic base oil may be used alone or in combination of two or more, or a mineral oil base oil may be used. One type or two or more types of base oils and one or more types of synthetic base oils can be mixed and used.

The lower limit of the aromatic content of the lubricating base oil in the lubricating oil composition of the present invention is required to be 8.5% by weight or more, preferably 12.5% by weight, based on the total amount of the lubricating base oil. As mentioned above, More preferably, it is 15 mass% or more. Further, the upper limit of the aromatic content of the lubricating base oil is preferably 49% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less, based on the total amount of the lubricating base oil. When the aromatic content of the lubricating base oil is less than 8.5% by mass, the solubility of the additive and deposit precursor may be reduced. If it exceeds 49 mass%, there is a possibility that deposits will increase and ring sticking may occur due to deterioration of the lubricating oil.
In the present invention, the aromatic content means a value measured according to ASTM D 2007-93. In general, the aromatic component includes alkylbenzene, alkylnaphthalene, anthracene, phenanthrene, and alkylated products thereof, as well as compounds in which four or more benzene rings are condensed, pyridines, quinolines, phenols, naphthols, and the like. Aromatic compounds having atoms are included.

The kinematic viscosity at 100 ° C. of the lubricating base oil according to the present invention is not particularly limited, but is preferably 40 mm ² / s or less, more preferably 35 mm ² / s or less, still more preferably 30 mm ² / s or less, particularly preferably 20 mm. ² / s or less. On the other hand, the kinematic viscosity at 100 ° C. is preferably 4 mm ² / s or more, more preferably 6 mm ² / s or more, and still more preferably 8 mm ² / s or more. The kinematic viscosity at 100 ° C. here refers to the kinematic viscosity at 100 ° C. as defined in ASTM D-445. When the kinematic viscosity at 100 ° C. of the lubricating base oil exceeds 40 mm ² / s, the low-temperature viscosity characteristics may be deteriorated, and when it is less than 4 mm ² / s, the oil film formation at the lubrication point is insufficient. Therefore, the lubricity is inferior, and the evaporation loss of the lubricating oil composition may increase.

The kinematic viscosity at 40 ° C. of the lubricating base oil according to the present invention is not particularly limited, but is preferably 700 mm ² / s or less, more preferably 570 mm ² / s or less, still more preferably 450 mm ² / s or less, particularly preferably. Is 240 mm ² / s or less. On the other hand, the kinematic viscosity at 40 ° C. is preferably 20 mm ² / s or more, more preferably 30 mm ² / s or more, and further preferably 80 mm ² / s or more. If the kinematic viscosity at 40 ° C. of the lubricating base oil exceeds 700 mm ² / s, the low-temperature viscosity characteristics may deteriorate, and if it is less than 20 mm ² / s, oil film formation at the lubrication site is insufficient. Therefore, the lubricity is inferior, and the evaporation loss of the lubricating oil composition may increase.

The viscosity index of the lubricating base oil according to the present invention is preferably 85 or more, more preferably 90 or more, and still more preferably 95 or more. The upper limit of the viscosity index is not particularly limited, and normal paraffin, slack wax, GTL wax, etc., or isoparaffin mineral oil obtained by isomerizing these can also be used.
The viscosity index in the present invention means a viscosity index measured according to JIS K 2283-1993.

Moreover,% C _A of the lubricating base oil of the present invention is preferably at least 1.9, more preferably 2.7 or more, further preferably 3.7 or more. When% C _A of the lubricating base oil is less than 1.9, antioxidant effect is not sufficiently obtained fear. Incidentally, say% _{C A} in the present invention is obtained by a method in accordance with ASTM D 3238-85 (n-d- M ring analysis), it means a percentage of the total number of carbon atoms of the aromatic carbon atoms.

In the lubricating oil composition of the present invention, an alkaline earth metal phenate (hereinafter referred to as phenate metal detergent (A)) is contained as an essential component as the component (A). The phenate-based metal detergent (A) is, for example, an alkylphenol having a structure represented by the following formulas (1) to (3), an alkylphenol sulfide, an alkaline earth metal salt of a Mannich reaction product of an alkylphenol, or a (over) basic thereof. It is a phenate-type metal detergent containing a salt.
Examples of the alkaline earth metal include magnesium, barium, and calcium. Magnesium or calcium is preferable, and calcium is particularly preferable.

In the general formulas (1) to (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may be the same or different and each has 4 to 30 carbon atoms, preferably Represents a 6-18 linear or branched alkyl group. If the carbon number is shorter than 4, the solubility in the lubricating base oil may be poor. If the carbon number is longer than 30, the production is difficult and the heat resistance may be poor. Specific examples of R ¹ to R ⁷ include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, Heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, etc. But it may be branched. These may also be primary alkyl groups, secondary alkyl groups or tertiary alkyl groups.
M ¹ , M ² and M ³ each represent an alkaline earth metal, preferably calcium and / or magnesium, x, y and z each independently represent an integer of 1 to 3, and m represents 0, 1 or 2 , N represents 0 or 1.

The base number of the phenate-based metal detergent (A) is preferably in the range of 50 to 400 mgKOH / g, more preferably in the range of 100 to 350 mgKOH / g, and still more preferably in the range of 120 to 300 mgKOH / g. When the base number is less than 50 mgKOH / g, corrosion wear may increase, and when it exceeds 400 mgKOH / g, there may be a problem in solubility.
The base number referred to here is JIS K2501 “Petroleum products and lubricants-Neutralization number test method”. Means the base number measured by the perchloric acid method according to the above.

The metal ratio of the phenate-based metal detergent (A) is not particularly limited, but the lower limit is 1 or more, preferably 2 or more, particularly preferably 2.5 or more, and the upper limit is preferably 20 or less, more preferably 15 or less, particularly It is desirable to use 10 or less. The metal ratio here is represented by the valence of the metal element in the phenate-based metal detergent (A) × metal element content (mol%) / soap group content (mol%). Alkaline earth metals such as calcium and magnesium, and soap groups mean phenol groups.

In the lubricating oil composition of the present invention, the content ratio of the component (A) needs to be 0.005 mol / kg or more, preferably 0.01 mol / kg as the soap content, based on the total amount of the composition. kg or more, more preferably 0.015 mol / kg or more. If the content is less than 0.005 mol / kg, the required heat resistance and anti-scuffing properties may not be obtained.

In the lubricating oil composition of the present invention, a metal detergent other than the phenate metal detergent (A) can be contained in order to adjust the base number of the lubricating oil composition. Specifically, one or more metal detergents selected from sulfonate detergents, salicylate detergents, carboxylate detergents, and phosphonate detergents can be used.

Examples of the sulfonate detergent include an alkali metal salt or an alkaline earth metal salt of an alkyl aromatic sulfonic acid obtained by sulfonating an alkyl aromatic compound having a molecular weight of 300 or more, preferably 400 to 700, and / or its ( Per) basic salts can be used. Examples of the alkali metal or alkaline earth metal include sodium, potassium, magnesium, barium, and calcium. Magnesium and / or calcium are preferable, and calcium is particularly preferably used.

Specific examples of the alkyl aromatic sulfonic acid include so-called petroleum sulfonic acid and synthetic sulfonic acid. As the petroleum sulfonic acid here, generally used is a product obtained by sulfonating an alkyl aromatic compound of a lubricating oil fraction of mineral oil, or so-called mahoganic acid produced as a by-product when white oil is produced. In addition, as the synthetic sulfonic acid, for example, a sulfonated alkylbenzene having a linear or branched alkyl group, which is obtained as a by-product from an alkylbenzene production plant that is a raw material of a detergent or is obtained by alkylating polyolefin with benzene, is obtained. Or those obtained by sulfonating alkylnaphthalene such as dinonylnaphthalene. The sulfonating agent for sulfonating these alkyl aromatic compounds is not particularly limited, but usually fuming sulfuric acid or anhydrous sulfuric acid is used.

Examples of the salicylate detergent include alkali metal salicylates having one hydrocarbon group having 1 to 19 carbon atoms, alkaline earth metal salicylates and / or their (over) basic salts, and hydrocarbon groups having 20 to 40 carbon atoms. 1 alkali metal salicylate, alkaline earth metal salicylate and / or (over) basic salt thereof, alkali metal salicylate having 2 or more hydrocarbon groups having 1 to 40 carbon atoms, alkaline earth metal salicylate and / or Or the (over) basic salt (These hydrocarbon groups may be the same or different). Examples of the alkali metal or alkaline earth metal include sodium, potassium, magnesium, barium, and calcium. Magnesium and / or calcium are preferable, and calcium is particularly preferably used.

The base number of the metal detergent other than the phenate metal detergent (A) used in the present invention is preferably in the range of 100 to 500 mgKOH / g, and more preferably in the range of 120 to 450 mgKOH / g. More preferably, it is in the range of 150 to 400 mgKOH / g. When the base number of such a metal-based detergent is less than 100 mgKOH / g, corrosion wear may increase, and when it exceeds 500 mgKOH / g, there may be a problem in solubility. The metal ratio is not particularly limited, but the lower limit is 1 or more, preferably 2 or more, particularly preferably 2.5 or more, and the upper limit is preferably 20 or less, more preferably 15 or less, and particularly preferably 10 or less. It is desirable.

In the lubricating oil composition of the present invention, the content of the metal detergent other than the phenate metal detergent (A) is 0 to 30 in a form including a diluent such as a lubricant base oil, based on the total amount of the composition. % By mass, preferably 0 to 20% by mass, particularly preferably 0 to 15% by mass.

The lubricating oil composition of the present invention contains an amine antioxidant as an essential component as the component (B). Specific examples of the amine-based antioxidant in the present invention include diphenylamine (hereinafter simply referred to as diphenylamine) containing 1 or 2 alkyl groups having 4 to 20 carbon atoms and N-phenyl-α. -Naphthylamine can be mentioned, but diphenylamine is preferred.

The position of the substituent of diphenylamine may be any position on the benzene ring, and when it has two or more alkyl groups, these alkyl groups may be on any benzene ring. The alkyl group preferably has 4 to 20 carbon atoms, more preferably 4 to 15 carbon atoms, and still more preferably 4 to 12 carbon atoms. When the number of carbon atoms is less than 4, the antioxidant property may be insufficient, and when the number of carbon atoms exceeds 20, production may be difficult, which is not preferable.

Specific examples of the diphenylamine include linear or branched dibutyldiphenylamine, linear or branched dioctyl diphenylamine, linear or branched dinonyl diphenylamine, linear or branched didecyl diphenylamine, or a mixture thereof. Of these, dibutyldiphenylamine or dioctyldiphenylamine is preferred.

The content of the component (B) in the present invention is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and further preferably 0.2% by mass or more based on the total amount of the composition. In particular, it is 0.3% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 2% by mass or less. When the content is less than 0.1% by mass, the thermal / oxidative stability of the lubricating oil composition tends to be insufficient. On the other hand, when content of (B) component exceeds 5 mass%, it exists in the tendency for the storage stability of a lubricating oil composition to fall.

The lubricating oil composition of the present invention contains an oil-soluble molybdenum compound as an essential component as the component (C). Examples of the oil-soluble molybdenum compound in the present invention include organic molybdenum compounds containing sulfur such as molybdenum dithiophosphate (MoDTP) and molybdenum dithiocarbamate (MoDTC), molybdenum compounds (for example, molybdenum oxide such as molybdenum dioxide and molybdenum trioxide, ortho Molybdic acid such as molybdic acid, paramolybdic acid, (poly) sulfurized molybdic acid, metal salts of these molybdates, molybdates such as ammonium salts, molybdenum disulfide, molybdenum trisulfide, molybdenum pentasulfide, polysulfide molybdenum, etc. Molybdenum sulfide, sulfurized molybdenum acid, metal salts or amine salts of sulfurized molybdenum acid, molybdenum halides such as molybdenum chloride, etc.) and sulfur-containing organic compounds (eg, alkyl (thio) xanthate, thiadiazole, mel Ptothiadiazole, thiocarbonate, tetrahydrocarbyl thiuram disulfide, bis (di (thio) hydrocarbyl dithiophosphonate) disulfide, organic (poly) sulfide, sulfide ester, etc.) or other organic compounds, or the above A complex of a sulfur-containing molybdenum compound such as molybdenum sulfide or sulfurized molybdenum acid and an alkenyl succinimide can be given.

As the oil-soluble molybdenum compound, an oil-soluble molybdenum compound that does not contain sulfur as a constituent element can be used. Specific examples of organic molybdenum compounds that do not contain sulfur as a constituent element include molybdenum-amine complexes, molybdenum-succinimide complexes, molybdenum salts of organic acids, and molybdenum salts of alcohols. Complexes, molybdenum salts of organic acids and molybdenum salts of alcohols are preferred.

Among these oil-soluble molybdenum compounds, MoDTC and / or MoDTP are preferable, and MoDTC is most preferable.

The content ratio when the component (C) is contained in the lubricating oil composition of the present invention is required to be 30 to 500 ppm by mass in terms of molybdenum element, based on the total amount of the composition. The lower limit of the content in terms of molybdenum element is preferably 50 ppm by mass or more, more preferably 80 ppm by mass or more, and the upper limit of the content is preferably 400 ppm by mass or less, more preferably 300 ppm by mass or less. It is. If the content in terms of molybdenum element is less than 30 ppm by mass, sufficient scuffing resistance may not be obtained, and if the content exceeds 500 ppm by mass, cleanliness may be adversely affected.

The lubricating oil composition of the present invention is an optional component commonly used in lubricating oils depending on its purpose in order to further improve its performance or to add other required performance in addition to the above configuration. Further additives can be added. Such additives include, for example, ashless dispersants, antioxidants, friction modifiers, viscosity index improvers, corrosion inhibitors, rust inhibitors, demulsifiers, metal deactivators, pour point depressants, Examples thereof include additives such as foaming agents and coloring agents.

The lubricating oil composition of the present invention can contain an ashless dispersant as the component (D).
As the ashless dispersant, any ashless dispersant used in lubricating oils can be used. For example, a linear or branched alkyl group or alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350 carbon atoms, is included in the molecule. Examples thereof include at least one nitrogen-containing compound or a derivative thereof, a Mannich dispersant, or a modified product of alkenyl succinimide. In use, one kind or two or more kinds arbitrarily selected from these can be blended.
In the case where the carbon number of the alkyl group or alkenyl group of the nitrogen-containing compound or derivative thereof is less than 40, the solubility in the lubricating oil base oil is reduced, whereas when the carbon number of the alkyl group or alkenyl group exceeds 400 The low-temperature fluidity of the lubricating oil composition is deteriorated, which is not preferable. The alkyl group or alkenyl group may be linear or branched, but preferable examples are derived from olefin oligomers such as propylene, 1-butene and isobutylene, and co-oligomers of ethylene and propylene. Examples include branched alkyl groups and branched alkenyl groups.

As the ashless dispersant, for example, one or more compounds selected from the following components (D-1) to (D-3) can be used.
(D-1) A succinimide having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof,
(D-2) benzylamine having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof,
(D-3) A polyamine having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof.

Examples of the component (D-1) include compounds represented by the following formula (4) or (5).

In the formula (4), R ¹ represents an alkyl group or alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350, and h represents an integer of 1 to 5, preferably 2 to 4. On the other hand, in the formula (5), R ² and R ³ each independently represents an alkyl group or an alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350 carbon atoms, and particularly preferably a polybutenyl group. I represents an integer of 0 to 4, preferably 1 to 3.

The component (D-1) includes a so-called monotype succinimide represented by the formula (4) in which succinic anhydride is added to one end of the polyamine, and a formula (5) in which succinic anhydride is added to both ends of the polyamine. The so-called bis-type succinimide represented by) is included, and the lubricating oil composition of the present invention may contain any of them or a mixture thereof. More preferably.
Specific examples of the polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.

Specific examples of the component (D-2) include compounds represented by the following formula (6).

In the formula (6), R ⁴ represents an alkyl or alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350 carbon atoms, and j represents an integer of 1 to 5, preferably 2 to 4.
There are no particular restrictions on the method for producing the benzylamine component (D-2). For example, a polyolefin such as a propylene oligomer, polybutene, or ethylene-α-olefin copolymer is reacted with phenol to obtain an alkylphenol. This is obtained by reacting formaldehyde with a polyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, or pentaethylenehexamine by a Mannich reaction.

Specific examples of the component (D-3) include compounds represented by the following formula (7).
R ⁵ —NH— (CH ₂ CH ₂ NH) _k —H (7)
In the formula (7), R ⁵ represents an alkyl group or alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350, and k represents an integer of 1 to 5, preferably 2 to 4.
There is no particular limitation on the method for producing the polyamine which is the component (D-3). For example, after chlorinating a polyolefin such as a propylene oligomer, polybutene, and an ethylene-α-olefin copolymer, ammonia, ethylenediamine, diethylenetriamine is added thereto. , Triethylenetetramine, tetraethylenepentamine, or a polyamine such as pentaethylenehexamine.

As a derivative of the nitrogen-containing compound mentioned as an example of the ashless dispersant, for example, boric acid is allowed to act on the aforementioned nitrogen-containing compound to neutralize part or all of the remaining amino group and / or imino group Or amidated so-called boron-modified compounds; 2 carbon atoms such as monocarboxylic acids (fatty acids, etc.) having 1 to 30 carbon atoms, oxalic acid, phthalic acid, trimellitic acid, pyromellitic acid, etc. A part of the remaining amino group and / or imino group by the action of a polycarboxylic acid of 30 to 30 or an anhydride thereof, or an ester compound, an alkylene oxide having 2 to 6 carbon atoms, hydroxy (poly) oxyalkylene carbonate, etc. Or a neutralized or amidated modified compound with a so-called oxygen-containing organic compound; the above-mentioned nitrogen-containing compound is reacted with phosphoric acid to remain A so-called phosphoric acid-modified compound obtained by neutralizing or amidating part or all of the amino group and / or imino group; a sulfur-modified compound obtained by allowing a sulfur compound to act on the nitrogen-containing compound described above; and the nitrogen-containing compound described above Examples of the compound include a modified compound in which two or more kinds of modifications selected from boron modification, modification with an oxygen-containing organic compound, phosphoric acid modification, and sulfur modification are combined.

When the ashless dispersant is contained in the lubricating oil composition of the present invention, the content is preferably 1 to 8% by mass based on the total amount of the composition.

The lubricating oil composition of the present invention can contain an extreme pressure agent. As the extreme pressure agent that can be used, any extreme pressure agent / antiwear agent used for lubricating oil can be used. For example, sulfur-based, phosphorus-based, sulfur-phosphorus extreme pressure agents and the like can be used. Specifically, phosphites, thiophosphites, dithiophosphites, trithiophosphites Esters, phosphate esters, thiophosphate esters, dithiophosphate esters, trithiophosphate esters, amine salts thereof, metal salts thereof, derivatives thereof, dithiocarbamate, zinc dithiocarbamate, molybdenum dithiocarbamate, disulfide , Polysulfides, sulfurized olefins, sulfurized fats and oils, and the like.
In the present invention, it is preferable to use zinc dithiophosphate and / or polysulfides as the extreme pressure agent / antiwear agent.

In the lubricating oil composition of the present invention, when an extreme pressure agent is used, its content is not particularly limited, but is preferably 0.05 to 5% by mass, more preferably 0.1%, based on the total amount of the composition. It is ˜2% by mass, particularly preferably 0.2 to 1% by mass. In the present invention, when an extreme pressure agent is contained, when it is less than 0.05% by mass, there is little effect of further improving wear prevention and seizure resistance, while when it exceeds 5% by mass, High temperature cleanliness is greatly deteriorated, which is not preferable. *

As the antioxidant, in addition to the amine-based antioxidant of the component (B), a phenol-based antioxidant, a copper-based, a molybdenum-based or other metal-based antioxidant can be contained. The content in the case of using these antioxidants is usually 0.1 to 5% by mass based on the total amount of the composition.
Examples of the friction modifier include ashless friction modifiers such as fatty acid esters, aliphatic amines, and fatty acid amides, and metal friction modifiers such as molybdenum dithiocarbamate and molybdenum dithiophosphate. When the friction modifier is used, the content is usually 0.1 to 5% by mass based on the total amount of the composition.

As the viscosity index improver, polymethacrylate viscosity index improver, olefin copolymer viscosity index improver, styrene-diene copolymer viscosity index improver, styrene-maleic anhydride copolymer viscosity index improver or poly Examples thereof include alkylstyrene viscosity index improvers. The mass average molecular weight of these viscosity index improvers is usually 10,000 to 1,000,000, preferably 50,000 to 500,000. When the viscosity index improver is used, the content is usually 0.1 to 20% by mass based on the total amount of the composition.

Examples of the corrosion inhibitor include benzotriazole, tolyltriazole, thiadiazole, and imidazole compounds.
Examples of the rust preventive include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, polyhydric alcohol ester and the like.
Examples of the demulsifier include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl naphthyl ether.

Examples of metal deactivators include imidazoline, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazoles or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5-bis. Examples thereof include dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, β- (o-carboxybenzylthio) propiononitrile.
Examples of the antifoaming agent include silicone oil having a kinematic viscosity at 25 ° C. of 100 to 100,000 mm ² / s, alkenyl succinic acid derivative, ester of polyhydroxy aliphatic alcohol and long chain fatty acid, methyl salicylate and o- Hydroxybenzyl alcohol, aluminum stearate, potassium oleate, N-dialkyl-allylamine nitroaminoalkanol, aromatic amine salt of isoamyl octyl phosphate, alkylalkylene diphosphate, metal derivative of thioether, metal derivative of disulfide, aliphatic hydrocarbon Fluorine compounds, triethylsilane, dichlorosilane, alkylphenyl polyethylene glycol ether sulfide, fluoroalkyl ether and the like can be mentioned.

When these additives are contained in the lubricating oil composition of the present invention, the content is based on the total amount of the composition, and is usually 0.005 to 5% by mass for the corrosion inhibitor, the rust inhibitor, and the demulsifier, The metal deactivator is usually selected from the range of 0.005 to 1% by mass, and the antifoaming agent is usually selected from the range of 0.0005 to 1% by mass.

Incidentally, the kinematic viscosity at 100 ° C. of the lubricating oil composition of the present invention is required to be 12.6 mm ² / s or more, preferably 13 mm ² / s or more, more preferably 14 mm ² / s or more. When the kinematic viscosity at 100 ° C. is less than 12.6 mm ² / s, the oil film forming ability is insufficient, and scuffing and excessive wear may occur.

In addition, the base number of the lubricating oil composition of the present invention is 20 to 100 mgKOH / in order to add high temperature cleanliness and acid neutralization performance even when using a high sulfur fuel containing asphaltenes. The lower limit is more preferably 25 mgKOH / g or more, still more preferably 30 mgKOH / g or more, and the upper limit is more preferably 90 mgKOH / g or less, still more preferably 80 mgKOH / g or less. If it is less than 20 mgKOH / g, the neutralizing power of an acidic substance such as sulfuric acid generated by the combustion of fuel is not sufficient, and corrosive wear may increase. If it exceeds 100 mgKOH / g, it is not only excessive for neutralization of acidic substances such as sulfuric acid generated by the combustion of fuel, but excessive base may accumulate on the piston as ash and cause excessive wear such as scuffing. is there.

The metal amount of the lubricating oil composition of the present invention is not particularly limited, but the lower limit is preferably 0.2% by mass or more, more preferably 0.4% by mass or more, and further preferably 0.7% by mass or more. The upper limit is preferably 3.6% by mass or less, more preferably 3.2% by mass or less, and still more preferably 2.9% by mass or less. When the metal content is less than 0.2% by mass, the neutralizing power of the acidic substance generated by combustion is not sufficient, and the high temperature cleanliness is not sufficiently exhibited. On the other hand, if it exceeds 3.6% by mass, the ash after adhering to the piston and burning adheres to the piston and increases the wear of the cylinder, which is not preferable.

The amount of sulfated ash in the lubricating oil composition of the present invention is not particularly limited, but the lower limit is preferably 1.2% by mass or more, more preferably 2% by mass or more, and particularly preferably 3% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less. The sulfated ash referred to here is JIS K2272 5. The value measured by the method specified in “Testing method for sulfated ash” is mainly attributable to the metal-containing additive.

Hereinafter, the content of the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these.

(Examples 1 to 16, Comparative Examples 1 to 13)
The lubricating oil compositions of the present invention (Examples 1 to 16) and comparative lubricating oil compositions (Comparative Examples 1 to 13) shown in Table 1 and Table 2 were prepared, respectively. The obtained compositions were evaluated for oxidation stability and scuffing resistance by PDSC oxidation stability test and high temperature extreme pressure test, respectively, and the results are also shown in Table 1 and Table 2. For Examples 1 to 15 and Comparative Examples 1 to 12, the mixing ratio of the two base oils so that the kinematic viscosity at 100 ° C. of the composition with the additive added was 20.5 mm ² / s. Adjusted. Further, a metal detergent was blended so that the base number of the composition was 40 mgKOH / g.

(Base oil)
Base oil A: 500 neutral (kinematic viscosity @ 100 ° C .: 10.8 mm ² / s, viscosity index: 97, aromatic content: 32.2% by mass,% C _A : 7.4%)
Base oil B: 150 bright stock (kinematic viscosity @ 100 ° C .: 31.5 mm ² / s, viscosity index: 96, aromatic content: 35.7 mass%,% C _A : 7.4%)
Base oil C: 250 neutral (kinematic viscosity @ 100 ° C .: 7.1 mm ² / s, viscosity index: 96, aromatic content: 34.9% by mass,% C _A : 9.3%)
Base oil D: Poly-α-olefin (PAO) 10 (kinematic viscosity @ 100 ° C .: 10 mm ² / s)
Base oil E: Poly-α-olefin (PAO) 40 (kinematic viscosity @ 100 ° C .: 39 mm ² / s)
(Additive)
1) Metal-based detergent (A) Calcium phenate (calcium content: 9.2% by mass, base number: 250 mgKOH / g, metal ratio: 3.6)
Calcium sulfonate (calcium content: 15.5% by mass, base number 400 mgKOH / g)
Calcium salicylate (calcium content: 8.2% by mass, base number 230 mgKOH / g)
2) Antioxidant (B-1) Diphenylamine (octyl / t-butyl mixture)
(B-2) N-phenyl-α-naphthylamine phenolic antioxidant (hindered phenol)
3) Oil-soluble molybdenum compound (C-1) MoDTC (molybdenum content 10% by mass)
(C-2) MoDTP (molybdenum content 8 mass%)
(C-3) Organic molybdenum complex (molybdenum content 1.1% by mass)
(C-4) Molybdenum-amine complex (molybdenum content 10% by mass)
4) Ashless dispersant (alkenyl succinimide, bis type, nitrogen content: 1% by mass)
5) Zinc dialkyldithiophosphate (ZnDTP) (2-ethylhexyl, zinc content 9.0% by mass, phosphorus content 7.4% by mass)
6) Zinc dialkyldithiocarbamate (ZnDTC) (amyl, zinc content 6.5% by mass, sulfur content 12.0% by mass)

(PDSC oxidation stability test)
5 mg of sample oil is sampled, oxidized at a temperature of 200 ° C. in an oxygen atmosphere at a pressure of 2 MPa, and the time until sudden heat generation occurs due to the oxidation is defined as PDSC induction time.
(High temperature extreme pressure test)
Evaluation was performed by a reciprocating friction and wear tester (TE77 manufactured by Plint). At a load of 200 N, an amplitude of 15 mm, and a vibration frequency of 50 Hz, the test piece temperature is increased from room temperature to 350 ° C. at a rate of temperature increase of 5 ° C./min, and the coefficient of friction is measured. The temperature at which the coefficient of friction rapidly increases is referred to as TE77 scuffing resistance temperature.

As is clear from the results in Tables 1 and 2, the lubricating oil composition of the present invention shows good results in both the PDSC oxidation stability test and the high temperature extreme pressure test. On the other hand, when no phenate-based metal detergent is contained (Comparative Examples 6 and 7), when no amine-based antioxidant is contained (Comparative Examples 1, 3 to 5 and 12), when no oil-soluble molybdenum compound is contained (Comparative Examples 1 to 3, 8 to 9 and 12) and the case of using a base oil with a low aromatic content (Comparative Examples 10 and 11), results of either or both of oxidation stability and scuffing resistance Inferior. When the kinematic viscosity at 100 ° C. is less than 12.6 (Comparative Example 13), the scuffing resistance is poor.

The lubricating oil composition of the present invention has excellent heat resistance and is suitable as a cylinder lubricating oil composition for a cross-head type diesel engine. In particular, the latest average piston speed is 8 m / s or more, more preferably 8.5 m / s. s or more, an extremely long stroke, combustion pressure is net effective pressure (BMEP) of 1.8 MPa or more, further 1.9 MPa or more, maximum cylinder wall temperature 230 ° C. or more, further 250 ° C. or more, especially 270 ° C. The cylinder lubricant composition for an electronically controlled two-stroke cycle diesel engine that is operated under a condition satisfying any or all of the above conditions exhibits a particularly excellent effect. The lubricating oil composition of the present invention can also be used as various marine diesel engine oils other than crosshead type diesel engine cylinder oils and cogeneration diesel engine oils.

Claims

(A) Alkaline earth metal phenate as a phenate soap component in a base oil having an aromatic content of 8.5% by mass or more based on the total amount of the composition, and (B) an amine. Containing 0.1 to 5% by mass of a system antioxidant and (C) 30 to 500 ppm by mass of an oil-soluble molybdenum compound in terms of molybdenum element, and having a base number of 20 to 100 mgKOH / g and 100 ° C. A cylinder lubricating oil composition for a crosshead type diesel engine, having a viscosity of 12.6 mm 2 / s or more.
2. The cylinder lubricant composition for a crosshead type diesel engine according to claim 1, wherein (B) the amine antioxidant is alkyldiphenylamine and / or N-phenyl-α-naphthylamine.
(C) The oil-soluble molybdenum compound is molybdenum dithiocarbamate and / or molybdenum dithiophosphate, and the cylinder lubricating oil composition for a crosshead type diesel engine according to claim 1 or 2.
The cylinder lubricating oil composition for a crosshead type diesel engine according to any one of claims 1 to 3, further comprising (D) an ashless dispersant in an amount of 1 to 8% by mass based on the total amount of the composition.